CN108341953B - Preparation method of sulfur-containing modified MQ silicon resin - Google Patents
Preparation method of sulfur-containing modified MQ silicon resin Download PDFInfo
- Publication number
- CN108341953B CN108341953B CN201711500599.5A CN201711500599A CN108341953B CN 108341953 B CN108341953 B CN 108341953B CN 201711500599 A CN201711500599 A CN 201711500599A CN 108341953 B CN108341953 B CN 108341953B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- containing heterocyclic
- containing modified
- modified
- heterocyclic group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
Abstract
The invention discloses a preparation method of sulfur-containing modified MQ silicon resin, which comprises the following steps: the preparation method is characterized in that a sulfur-containing heterocyclic monomer, alkyl orthosilicate and an organic solvent are mixed, an acidic stabilizer and a catalyst are added, water is added dropwise for modification reaction, and then an end capping agent is added for polymerization reaction to obtain the sulfur-containing modified MQ silicon resin.
Description
Technical Field
The invention belongs to the technical field of organic silicon materials, and relates to a preparation method of sulfur-containing modified MQ silicon resin.
Technical Field
The application field of optical materials is widening, products are continuously developed towards high refractive index, high light transmittance and high reliability, and organic silicon materials are widely applied to the preparation field of optical materials such as medicine, biology, communication and the like due to good temperature resistance, mechanical properties and non-toxicity and environmental protection. The organosilicon materials applied in the fields of optical lenses, optical fiber materials and the like at present require higher refractive index, even more than 1.7, and simultaneously have good mechanical properties.
The method for improving the refractive index of the organic silicon material in the prior art is mainly to introduce a high-refractive-index group into the molecular structure of polysiloxane resin, and comprises the following steps:
(1) the refractive index can be improved by introducing aromatic compounds or condensed ring compounds, but the prepared polymer has large dispersion and hard and brittle defects in the aspect of mechanical properties, and the refractive index can only reach about 1.5.
(2) However, the resin has a high density and is inferior in weather resistance and easy to be yellowed.
(3) Introduction of heavy metal ions, e.g. lead, lanthanum or TiO2PbS and FeS nanoparticles are used to increase the refractive index, but the resin has high density, low impact resistance, easy yellowing and poor practicability.
(4) The introduction of the aliphatic polycyclic compound can improve the refractive index and lower the dispersion.
In addition, the refractive index can be improved by introducing hetero elements such as sulfur, nitrogen, phosphorus and the like, while the introduction of sulfur in the polymer is the most effective method for improving the refractive index, and the obtained material has small dispersion and good environmental stability.
However, the existing method for introducing sulfur element through a sulfur heterocyclic monomer is a Grignard reaction preparation under an ultralow temperature condition, and has the defects of large product odor and harsh preparation conditions, which limits the application and popularization of the high-refractive-index silane and the resin.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the sulfur-containing modified MQ silicon resin and the preparation method thereof, the sulfur-containing modified MQ silicon resin is prepared by adopting an improved preparation method, the stability of a sulfur-containing heterocyclic group in the synthesis process is obviously improved, and the prepared resin has the advantages of small smell, good compatibility with organic silicon resin, mild preparation conditions and simple process.
The purpose of the invention is realized by the following technical scheme:
a sulfur-containing modified MQ silicone resin having an average compositional formula as shown in formula 1: (R)1SiO3/2)a(R1 2SiO)b(SiO2)c(R1 3SiO1/2)d(R2R3R4SiO1/2)e(formula 1);
the R is1Has a structural formula of-OR0Said R is0Containing a sulfur-containing heterocyclic group having n sulfur atoms, n being an integer multiple of 2; the R is2、R3、R4Are identical or different hydrogen groups, monovalent hydrocarbon groups free of aliphatic unsaturation, or alkenyl groups having 2 to 10 carbon atoms;
the a, c and e are numbers which are more than 0 and less than 1, the b and d are numbers which are more than or equal to 0 and less than 1, and the (a +2b +3d)/(a + b + c + d) is 0.7-1.5, the e/(a + b + c + d) is 0.1-0.5, and the a + b + c + d + e is 1.
Preferably, (a +2b +3d + e)/(a + b + c + d) is 1.2 to 1.6.
Preferably, all other atoms in the sulfur-containing heterocyclic group are carbon atoms. More preferably, the sulfur-containing heterocyclic group is a saturated sulfur-containing heterocyclic group. More preferably, the sulfur-containing heterocyclic group has a symmetrical structure.
More preferably, R is0Is composed of
One or more of them.
The monovalent hydrocarbon group having no aliphatic unsaturated bond may be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or similar alkyl groups; cyclopentyl, cyclohexyl, or similar cycloalkyl groups; phenyl, tolyl, xylyl, or similar aryl groups; benzyl, phenethyl, phenylpropyl, or similar aralkyl groups; 3,3, 3-trifluoropropyl, 3-chloropropyl or similar haloalkyl; most preferred above are alkyl and aryl groups, especially methyl and phenyl. Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group and the like, and among them, a vinyl group is preferable.
Preferably, the dynamic viscosity value of the sulfur-containing modified MQ silicon resin at 25 ℃ is 10000-20000 mPa.
The invention further provides a preparation method of the sulfur-containing modified MQ silicon resin, which comprises the following steps:
mixing a sulfur-containing heterocyclic monomer, alkyl orthosilicate and an organic solvent, adding an acidic stabilizer and a catalyst, dropwise adding water, performing a modification reaction, and then adding an end capping agent for a polymerization reaction to obtain sulfur-containing modified MQ silicon resin; the acidic stabilizer is organic acid with PKa being more than or equal to 0 and less than or equal to 3.0;
the sulfur-containing heterocyclic monomer is a monomer having at least oneA sulfur-containing heterocyclic group having n sulfur atoms, n being an integral multiple of 2, and at least one hydroxyl group; the structural formula of the alkyl orthosilicate is as follows: r2R3R4SiR1，R1、R2、R3、R4Are identical or different alkoxy groups of C1 to C5.
The PKa is the acidity coefficient of a substance at 25 ℃, reflects the acidity intensity of the substance, and the smaller the value is, the stronger the acidity is, and the value can be looked up by a physical property data manual or by querying the value according to a chemical substance registration number (CAS number).
Preferably, the alkyl orthosilicate is ethyl orthosilicate and/or methyl orthosilicate.
The end-capping agent is an end-capping agent commonly used in organosilicon synthesis and comprises a hydrocarbyl silane end-capping agent, a vinyl silane end-capping agent or a hydrogen-based silane end-capping agent, wherein the hydrocarbyl silane end-capping agent is one or more of hexamethyldisiloxane, hexaphenyldisiloxane, hexamethyldisilazane, trimethylmethoxysilane and trimethylethoxysilane; the vinyl silane end capping agent is ViMe2SiOSiMe2Vi、ViMe2SiNSiMe2Vi、ViMe2SiOMe、 ViMe2SiOEt、CH2＝CH-CH2Me2SiOEt、CH2＝CHMeCOOC3H6SiMe2One or more of OEt; the hydrosilane end-capping agent is HMe2SiOSiMe2H、HMe2SiNSiMe2H、HMe2One or more of SiOEt.
Preferably, the molar ratio of the sulfur-containing heterocyclic monomer, the alkyl orthosilicate and the end-capping agent is (0.7-1.5): 1: (0.1-0.5). More preferably, the ratio of the sum of the amounts of the sulfur-containing heterocyclic monomer and the blocking agent to the amount of the alkyl orthosilicate is (1.2 to 1.6): 1.
Preferably, all other atoms in the sulfur-containing heterocyclic group are carbon atoms. More preferably, the sulfur-containing heterocyclic group is a saturated sulfur-containing heterocyclic group. More preferably, the sulfur-containing heterocyclic group has a symmetrical structure.
More preferredThe sulfur-containing heterocyclic monomer is 1, 2-dithiane-4-methanol
1, 3-dithiane-2-carboxylic acid
4- (1, 3-dithiolane) phenol
1, 3-Dithiolan-2-ylmethanol
1, 4-dithiospiro [4.5 ]]-8-decanol
1, 4-dithiospiro [4.4 ]]Nonan-6-ylmethanol
6, 10-dithiospiro [4.5 ]]Decan-1-ols
6, 10-dithiospiro [4.5 ]]Decane-2-ol
One or more of them.
Preferably, the molar ratio of the water to the alkyl orthosilicate is (2-3): 1.
Preferably, the acidic stabilizer is a monocarboxylic acid. More preferably, the acidic stabilizer is one or more of dichloroacetic acid, trichloroacetic acid, 2-propiolic acid and pyruvic acid. More preferably, the mass of the acidic stabilizer is 2% to 8% of the mass of the sulfur-containing heterocyclic monomer. The invention can play a stabilizing role on the sulfur-containing heterocyclic groups by adding the acidic stabilizer, and effectively inhibit the ring-opening reaction of the sulfur-containing heterocyclic groups in the heating reaction process, thereby reducing the odor of the product and improving the reaction yield.
Preferably, the organic solvent is a mixture of an organic solvent A and an organic solvent B, the organic solvent A is insoluble or slightly soluble in water and has a boiling point less than 100 ℃, and is one or more of benzene, chloroform, dichloromethane, ethyl acetate, petroleum ether, diethyl ether, pentane, naphtha, cyclohexane, n-hexane, carbon tetrachloride, dichloroethane, trichloroethane, triethylamine and heptane; the organic solvent B is a water-miscible solvent with a boiling point less than 100 ℃, and is one or more of methanol, ethanol, ethylene glycol dimethyl ether, isopropanol, acetone, butanone and tetrahydrofuran.
Preferably, the amount of the organic solvent A is 1-3 times of the sum of the masses of the sulfur-containing heterocyclic monomer, the alkyl orthosilicate and the end-capping agent, and the amount of the organic solvent B is 0.5-1 time of the sum of the masses of the sulfur-containing heterocyclic monomer, the alkyl orthosilicate and the end-capping agent.
The kind of the catalyst is not particularly limited, and the catalyst can be one or more of common concentrated sulfuric acid with the mass fraction of 98%, concentrated hydrochloric acid with the mass fraction of 37%, trifluoromethanesulfonic acid or strong acid cation resin. The amount of the catalyst is not particularly limited, and is preferably 0.5 to 1% of the sum of the mass of the sulfur-containing heterocyclic monomer, the mass of the alkyl orthosilicate, and the mass of the end-capping agent.
Preferably, the temperature of the modification reaction is 80-110 ℃, and the time is 18-36 h.
Preferably, the polymerization reaction is carried out at 90-100 ℃ for 12-24 h.
After the polymerization reaction, the purified sulfur-containing modified MQ silicon resin is obtained through the operations of temperature reduction, neutralization, water washing, separation and the like. Preferably, the separation comprises first distillation, extraction and water washing, and then second distillation is carried out, wherein the first distillation is reduced pressure distillation at 30-40 ℃ and-0.095 MPa, and the first distillation can distill out alcohol in the system so as to prevent the extractant and the alcohol from forming a homogeneous phase and cannot obtain a good extraction effect.
Preferably, the extractant used for the extraction is ethyl acetate or n-hexane. Preferably, the mass of the extracting agent is 1-2 times of the sum of the mass of the sulfur-containing heterocyclic monomer, the mass of the alkyl orthosilicate and the mass of the end-capping agent.
Preferably, a demulsifier is added after the extractant is added during the extraction, and the demulsifier is petroleum ether or diethyl ether. The demulsifier is added during extraction to demulsify, so that the washing time can be effectively reduced, the washing efficiency can be improved, the layering can be accelerated, the product purity can be improved, and the post-treatment efficiency can be improved.
Preferably, the second distillation is conducted at 60 to 70 ℃ and-0.095 to-0.1 MPa under reduced pressure to remove the solvent. In a specific separation operation, the solvent is removed by rotary evaporation.
The invention has the beneficial effects that:
the synthesis of the prior sulfur-containing organosilicon material adopts Grignard reaction synthesis at low temperature, and is difficult to realize industrialization due to the requirement of ultra-low temperature reaction conditions, while the commonly used acid-catalyzed hydrolysis and condensation for organosilicon synthesis easily forms a monomer or a group with larger odor due to the easy ring opening of a sulfur-containing heterocycle under the conditions of heating and acid catalysis, so that the prepared high-refractive-index episulfide modified MQ resin has large odor and unstable storage. The preparation method of the invention adds the organic acid to carry out stable treatment on the sulfur-containing heterocycle in the reaction process, thereby preventing the ring opening of the sulfur-containing heterocycle, reducing the smell and improving the yield. The sulfur-containing heterocyclic ring modified MQ resin prepared by the improved process can be used as an additive or a synthetic raw material of optical materials such as organic silicon and the like and a component of a packaging material, so that the refractive index and the light transmittance of a product are improved.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. In the following examples, Me represents a methyl group, Vi represents a vinyl group, and Et represents an ethyl group.
Example 1
Ethyl acetate (382.45g), ethanol (191.2 g) were added to a four-necked flask equipped with a condenser, nitrogen inlet and constant pressure funnel3g) 1, 2-dithianon-4-methanol
(108.99g, 0.80mol) and tetraethoxysilane (208.33g, 1.00mol) are stirred for 40min, 1, 3-dithianon-2-yl methanol is completely dissolved, dichloroacetic acid (3.27g, 0.0254mol) and trifluoromethanesulfonic acid (2.29g, 0.0153mol) are added and stirred for 10min, water (36.00g, 2mol) is added and dripped into the reaction system in a constant pressure funnel at the speed of 5 drops/min, vinyl dimethylethoxysilane (ViMe) is added after reaction for 48h at 90 DEG C2SiOEt) (65.13g, 0.5mol), reflux reaction at 100 ℃ for 24h, cooling to room temperature, adding ammonium bicarbonate (4.18g, 0.0538mol), stirring for 10min, layering and taking oil layer, reduced pressure distillation at 30 ℃ and-0.095 MPa for 20min, adding ethyl acetate (382.45g), adding petroleum ether (114.74g) for demulsification, washing with deionized water to neutrality, layering and taking oil layer, and reduced pressure distillation at 65 ℃ and-0.095 MPa to obtain the sulfur-containing modified MQ silicone resin.
Example 2
Benzene (819.72g), isopropanol (245.92g), 1, 3-dithiane-2-carboxylic acid were added to a four-necked flask equipped with a condenser, nitrogen inlet and constant pressure funnel
(164.25g, 1.00mol) and tetraethoxysilane (208.33g, 1.00mol), stirring for 60min, adding 2-propiolic acid (8.21g, 0.1173mol) and 37 wt% concentrated hydrochloric acid (4.10g, 0.0415mol) after the 1, 3-dithiane-2-formic acid is completely dissolved, stirring for 30min, adding distilled water (54.00g, 3mol) into a constant pressure funnel, dripping into the reaction system at the speed of 7 drops/min, reacting for 24h at 100 ℃, adding tetramethyl divinyl disiloxane (ViMe)2SiOSiMe2Vi) (37.28g, 0.2mol), reflux reaction at 95 ℃ for 15h, cooling to room temperature, adding ammonium bicarbonate (15.07g, 0.1906mol), stirring for 20min, layering to obtain an oil layer, vacuum distilling at 35 ℃ and-0.095 MPa for 20min, adding n-hexane (532.82g), adding petroleum ether (204.93g) for demulsification, washing with deionized water to neutrality, layering to obtain an oil layer, and vacuum distilling at 65 ℃ and-0.095 MPa to obtain the sulfur-containing modified MQ silicone resin.
Example 3
Cyclohexane (1264.37g), tetrahydrofuran (337.17g), 4- (1, 3-dithiolane) phenol were charged in a four-necked flask equipped with a condenser tube, nitrogen inlet and constant pressure funnel
(237.97g, 1.2mol) and methyl orthosilicate (152.22g, 1.00mol) are stirred for 50min, after 4- (1, 3-dithiolane) phenol is completely dissolved, trichloroacetic acid (19.04g, 0.1165mol) and 98% wt concentrated sulfuric acid (3.37g, 0.0337mol) are added to be stirred for 30min, distilled water (54.00g, 3mol) are added to a reaction system in a constant pressure funnel at a speed of 10 drops/min, dimethyl ethoxysilane (31.27g, 0.3mol) is added to react for 36h at 100 ℃, reflux reaction is carried out for 12h at 90 ℃, cooling is carried out to room temperature, ammonium bicarbonate (20.36g, 0.2575mol) is added to be stirred for 30min, oil layers are taken by layering, reduced pressure distillation is carried out for 20min at 40 ℃ -0.095MPa, ethyl acetate (632.19g) is added, diethyl ether (210.73g) is added to emulsify, deionized water is used for washing to be neutral, oil layers are taken, reduced pressure distillation is carried out at 70 ℃ -0.095MPa, obtaining the sulfur-containing modified MQ silicon resin.
Example 4
In a four-necked flask equipped with a condenser tube, nitrogen inlet and constant pressure funnel were added ether (356.39g), methanol (356.39g), 1, 3-dithianon-2-ylmethanol
(190.74g, 1.40mol) and methyl orthosilicate (152.22g, 1.00mol) are stirred for 30min, after the 1, 3-dithianon-2-yl methanol is completely dissolved, pyruvic acid (9.54g, 0.1083mol) and 98% concentrated sulfuric acid (2.49g, 0.0249mol) are added and stirred for 30min, distilled water (36.00g, 2mol) is added into a reaction system in a constant pressure funnel at the speed of 8 drops/min and reacted for 40h at the temperature of 90 ℃, tetramethyl disiloxane (HMe) is added2SiOSiMe2H) (13.43g, 0.1mol), refluxing and reacting at 100 ℃ for 18h, cooling to room temperature, adding ammonium bicarbonate (18.76g, 0.2373mol), stirring for 10min, layering to obtain an oil layer, distilling at 40 ℃ and-0.095 MPa under reduced pressure for 20min, adding n-hexane (356.39g), adding ether (213.83g), demulsifying, washing with deionized water to neutrality, and dividing into fractionsAnd taking an oil layer, and carrying out reduced pressure distillation at 67 ℃ and-0.095 MPa to obtain the sulfur-containing modified MQ silicon resin.
Example 5
Chloroform (486.75g), methanol (227.15g), dithianon-4-carboxylic acid were added to a four-necked flask equipped with a condenser, nitrogen inlet and constant pressure funnel
(135.20g, 0.9mol) and methyl orthosilicate (152.22g, 1.00mol) are stirred for 40min, dichloroacetic acid (8.11g, 0.0629mol) and strong acid cation resin (3.24g) are added after dithiane-4-carboxylic acid is completely dissolved, stirred for 20min, distilled water (45.00g, 2.5mol) is added into a reaction system in a constant pressure funnel at the speed of 6 drops/min, after reaction is carried out for 45h at 95 ℃,1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane (ViMe) is added2SiNSiMe2Vi) (37.08g, 0.2mol), refluxing and reacting at 100 ℃ for 24h, cooling to room temperature, adding ammonium bicarbonate (5.97g, 0.0755mol), stirring for 20min, taking an oil layer by layer, distilling at 38 ℃ and 0.095MPa by reduced pressure for 20min, adding ethyl acetate (356.95g), adding diethyl ether (97.35g) for demulsification, washing with deionized water to neutrality, taking an oil layer by layer, and distilling at 70 ℃ and 0.095MPa by reduced pressure to obtain the sulfur-containing modified MQ silicon resin.
Comparative examples
Ethyl acetate (382.45g), ethanol (191.23g), 1, 3-dithianon-2-ylmethanol were placed in a four-necked flask equipped with a condenser, nitrogen inlet and constant pressure funnel
(108.99g, 0.80mol) and tetraethoxysilane (208.33g, 1.00mol) are stirred for 40min, after the 1, 3-dithianon-2-yl methanol is completely dissolved, trifluoromethanesulfonic acid (2.29g, 0.0153mol) is added and stirred for 10min, distilled water (36.00g, 2mol) is added and dripped into the reaction system in a constant pressure funnel at the speed of 5 drops/min, the reaction is carried out for 48h at the temperature of 90 ℃, and vinyl dimethylethoxysilane (ViMe) is added2SiOEt) (65.13g, 0.5mol), reflux reaction at 100 deg.C for 24h, cooling to room temperature, adding ammonium bicarbonate (4.18g, 0.0538mol), stirring for 10min, layering, and collecting oil layerAnd carrying out reduced pressure distillation at the temperature of 35 ℃ and the pressure of-0.095 MPa for 20min, adding ethyl acetate (382.45g), adding petroleum ether (114.74g) for demulsification, washing with deionized water to be neutral, layering, taking an oil layer, and carrying out reduced pressure distillation at the temperature of 66 ℃ and the pressure of-0.095 MPa to obtain the comparative sulfur-containing modified MQ silicon resin.
Test examples
The sulfur-containing modified MQ silicone resins prepared in examples 1 to 5 and comparative examples and the high-folding resin RH-SP605-3 (niverngbo standing grain high new materials, ltd) were subjected to performance tests:
1. gardner color: testing according to GB/T22295-;
2. odor intensity: testing according to GB/T14675;
3. viscosity: the dynamic viscosity value at 25 ℃ was tested in accordance with GB/T10247-1988;
4. refractive index: testing according to GB/T6488-;
5. light transmittance: the test was carried out according to GB/T2410-2008.
The test data are shown in Table 2, wherein the sulfur-containing modified MQ silicone resin prepared in the comparative example is shown as comparative 1, and the high-breaking resin RH-SP605-3 (Ningbo Runza high New materials Co., Ltd.) is shown as comparative 2.
TABLE 2
| Test items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Gardner color number | 1 | 1 | 1 | 1 | 1 | 3 | 1 |
| Strength of odor | 1 | 0 | 1 | 0 | 0 | 5 | 0 |
| Viscosity of the oil | 12500 | 15300 | 12000 | 15750 | 19800 | 18300 | 18500 |
| Refractive index | 1.6225 | 1.6490 | 1.6050 | 1.6330 | 1.6270 | 1.5830 | 1.5410 |
| Transmittance (a) | 97 | 98 | 96.5 | 95.5 | 95 | 92 | 93 |
As can be seen from the data in Table 2, the sulfur-containing modified MQ silicon resin prepared by the method disclosed by the invention is small in smell, high in refractive index and high in light transmittance, can be applied to preparation of optical materials such as LEDs and has a wide application prospect, and the preparation method is simple and has a good industrial prospect.
The influence of the sulfur-containing modified MQ silicone resin and high-folding resin RH-SP605-3 (nivernghe high new materials, ltd.) prepared in examples 1 to 5 and comparative example on the activity of platinum catalysts was also examined, and the test methods were described in references: preparation of graphite oxide supported platinum complex and performance study of catalytic olefin hydrosilylation reaction thereof, master thesis of Nanchang university, Hoffo): 200g of a base gum, which was obtained by mixing octene and triethoxysilane in a molar ratio of 1:1 and adding 5ppm of a platinum catalyst (Pt-vinylpolysiloxane complex, type DC4000, Dow Corning, platinum content 5000ppm), and 2g of the sulfur-containing modified MQ silicone resin prepared in examples 1 to 5, comparative 1, and comparative 2 were added to a beaker, respectively, and stirred uniformly to obtain a sulfur-containing base gum.
Heating the sulfur-containing base rubber to 60 ℃, reacting for 1h, and carrying out quantitative analysis by using Gas Chromatography (GC) to obtain the octane conversion rate and the yield of the addition product. Quantitative analysis by Gas Chromatography (GC) Using GC-2010 from Shimadzu, Japan, a 25 m.times.0.32 mm.times.0.5 μm Rtx-1 capillary column was used with a split ratio of 50: 1. The temperature rising procedure of the column box is as follows: stabilizing at 50 deg.C for 1min, heating to 260 deg.C at a rate of 15 deg.C/min, and maintaining at 260 deg.C for 10 min.
The data are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, the sulfur-containing modified MQ silicon resin prepared by the method has a remarkably reduced poisoning effect on a platinum catalyst, and is beneficial to application in an organosilicon material catalytically cured by the platinum catalyst.
Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and do not limit the protection scope of the present invention. It will be understood by those skilled in the art that various deductions and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of sulfur-containing modified MQ silicon resin comprises the following steps:
mixing a sulfur-containing heterocyclic monomer, alkyl orthosilicate and an organic solvent, adding an acidic stabilizer and a catalyst, dropwise adding water, performing a modification reaction, and then adding an end capping agent for a polymerization reaction to obtain sulfur-containing modified MQ silicon resin; the acidic stabilizer is an organic acid with PKa being more than or equal to 0 and less than or equal to 3.0, and the acidic stabilizer is carboxylic acid;
the sulfur-containing heterocyclic monomer is a compound having at least one sulfur-containing heterocyclic group and at least one hydroxyl group, the sulfur-containing heterocyclic group has n sulfur atoms, n is an integral multiple of 2, other atoms in the sulfur-containing heterocyclic group are all carbon atoms, and the sulfur-containing heterocyclic group is a saturated sulfur-containing heterocyclic group; the structural formula of the alkyl orthosilicate is as follows: r2R3R4SiR1，R1、R2、R3、R4Is the same or different alkoxy of C1-C5;
the sulfur-containing modified MQ silicone resin has an average composition formula as shown in formula 1:
(R1SiO3/2)a(R1 2SiO)b(SiO2)c(R1 3SiO1/2)d(R2R3R4SiO1/2)e(formula 1);
the R is1Has a structural formula of-OR0Said R is0Containing a sulfur-containing heterocyclic group having n sulfur atoms, n being an integer multiple of 2; the R is2、R3、R4Are identical or different hydrogen groups, monovalent hydrocarbon groups free of aliphatic unsaturation, or alkenyl groups having 2 to 10 carbon atoms;
the a, c and e are numbers which are more than 0 and less than 1, the b and d are numbers which are more than or equal to 0 and less than 1, and the (a +2b +3d)/(a + b + c + d) is 0.7-1.5, the e/(a + b + c + d) is 0.1-0.5, and the a + b + c + d + e is 1.
2. The method for preparing sulfur-containing modified MQ silicone resin according to claim 1, wherein the mass of the acidic stabilizer is 2 to 8% of the mass of the sulfur-containing heterocyclic monomer.
3. The method for preparing sulfur-containing modified MQ silicon resin according to claim 1, wherein the temperature of the modification reaction is 80 to 110 ℃ and the time is 18 to 36 hours.
4. The method for preparing sulfur-containing modified MQ silicone resin according to claim 1, wherein the sulfur-containing heterocyclic groups have a symmetrical structure.
5. The method for preparing sulfur-containing modified MQ silicone resin according to any one of claims 1 to 4, wherein the molar ratio of the sulfur-containing heterocyclic monomer, alkyl orthosilicate and capping agent is (0.7 to 1.5): 1: (0.1-0.5).
6. The method for preparing sulfur-containing modified MQ silicone resins of claim 5, wherein the sulfur-containing heterocyclic monomer is 1,2-Dithiolane-4-methanol
1, 3-dithiane-2-carboxylic acid
4- (1, 3-dithiolane) phenol
1, 3-Dithiolan-2-ylmethanol
1, 4-dithiospiro [4.5 ]]-8-decanol
1, 4-dithiospiro [4.4 ]]Nonan-6-ylmethanol
6, 10-dithiospiro [4.5 ]]Decan-1-ols
6, 10-dithiospiro [4.5 ]]Decane-2-ol
One or more of them.
7. The sulfur-containing modified MQ silicone resin prepared by the preparation method according to any one of claims 1 to 4, wherein the sulfur-containing modified MQ silicone resin has a 25 ℃ dynamic viscosity value of 10000 to 20000 mPas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711500599.5A CN108341953B (en) | 2017-12-30 | 2017-12-30 | Preparation method of sulfur-containing modified MQ silicon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711500599.5A CN108341953B (en) | 2017-12-30 | 2017-12-30 | Preparation method of sulfur-containing modified MQ silicon resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108341953A CN108341953A (en) | 2018-07-31 |
| CN108341953B true CN108341953B (en) | 2021-01-26 |
Family
ID=62961289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711500599.5A Active CN108341953B (en) | 2017-12-30 | 2017-12-30 | Preparation method of sulfur-containing modified MQ silicon resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108341953B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194826B (en) * | 2018-08-31 | 2021-10-26 | 广东工业大学 | Modified polysiloxane and application thereof |
| CN110194829B (en) * | 2018-08-31 | 2021-10-26 | 广东工业大学 | Preparation method of high-refractive-index PU (polyurethane) modified polysiloxane |
| CN113201138B (en) * | 2021-02-03 | 2022-11-22 | 惠州学院 | Transparent light-curable high-refractive-index mercapto silicone oil and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5723606A (en) * | 1980-07-18 | 1982-02-06 | Asahi Chem Ind Co Ltd | Polymerization of olefin |
| CN102015837A (en) * | 2008-05-15 | 2011-04-13 | 埃西勒国际通用光学公司 | Sulfur modified silanes for the elaboration of high refractive index materials |
| CN104583278A (en) * | 2012-05-14 | 2015-04-29 | 莫门蒂夫性能材料股份有限公司 | High refractive index material |
| CN107236131A (en) * | 2017-07-06 | 2017-10-10 | 华南师范大学 | A kind of super high molecular weight modified polyorganosiloxane and preparation method thereof |
-
2017
- 2017-12-30 CN CN201711500599.5A patent/CN108341953B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5723606A (en) * | 1980-07-18 | 1982-02-06 | Asahi Chem Ind Co Ltd | Polymerization of olefin |
| CN102015837A (en) * | 2008-05-15 | 2011-04-13 | 埃西勒国际通用光学公司 | Sulfur modified silanes for the elaboration of high refractive index materials |
| CN104583278A (en) * | 2012-05-14 | 2015-04-29 | 莫门蒂夫性能材料股份有限公司 | High refractive index material |
| CN107236131A (en) * | 2017-07-06 | 2017-10-10 | 华南师范大学 | A kind of super high molecular weight modified polyorganosiloxane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "含硫高折光树脂的研究进展";杨龙等;《化工新型材料》;20140630;第42卷(第6期);第15-17页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108341953A (en) | 2018-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108341953B (en) | Preparation method of sulfur-containing modified MQ silicon resin | |
| EP0694573B1 (en) | Branched organosilicon compounds and a method for their preparation | |
| KR101596971B1 (en) | Process for controlled hydrolysis and condensation of epoxy-functional organosilanes and the cocondensation thereof with further organofunctional alkoxysilanes | |
| US10023699B2 (en) | Curable siloxane compositions | |
| CN109824903B (en) | High-refractive-index boron-containing organic silicon tackifier and preparation method thereof | |
| CN108409778B (en) | Preparation method and application of high-refractive-index modified silane | |
| CN108997582B (en) | Preparation method of polysiloxane fluid containing active hydrogen at single end | |
| CN103242532A (en) | Preparation method of environment-friendly solventless liquid silicone resin | |
| CN108329474B (en) | Organic silicon resin for single-component addition type organic silicon impregnating varnish and preparation method and application thereof | |
| CN108610485B (en) | High-refractive-index organic silicon resin and preparation method thereof | |
| US11203606B2 (en) | Method for continuously producing low-alkoxy branched siloxanes | |
| CN111116918A (en) | Preparation method of organosilane oligomer | |
| JP5821971B2 (en) | Method for producing polysiloxane | |
| CN115466374B (en) | Polyhydroxy cyclic polymer/polysiloxane double-modified imidazole latent curing agent, and preparation method and application thereof | |
| CN109354687A (en) | A kind of alkoxy end-capped polysiloxanes, preparation method and application | |
| US7326766B2 (en) | Method for production of high solids silicone resin coating solution | |
| JP6048380B2 (en) | Organosilicon compound having oxetane ring and method for producing the same | |
| CN113881047A (en) | Narrow molecular weight distribution single-end hydroxyl-terminated polydimethylsiloxane and preparation method thereof | |
| DE2615077A1 (en) | PROCESS FOR THE PRODUCTION OF POLYSILOXANE POLYMERS HAVING FUNCTIONAL EPOXY GROUPS | |
| Obrezkova et al. | Hydrolytic polycondensation of sodiumoxymethyl (dialkoxy) silanes as a method for producing linear poly [(sodiumoxy) methylsilsesquioxane] | |
| CN115505126B (en) | Preparation method of beta-end siloxane-based polydimethylsiloxane | |
| US8524933B2 (en) | Beta-ketoester group-containing organopolysiloxane compound | |
| US11136436B2 (en) | Method for condensation polymerization of hydroxyl-terminated polydiorganosiloxanes | |
| CN116063681A (en) | Double-layer structure vinyl end capping Process for the preparation of polysiloxanes | |
| CN108467486B (en) | Sulfur poisoning resistant platinum catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |